5-Amino-2,3,7,8-tetrathiaalkane-1,9-dioic acids, esters and salts

ABSTRACT

The present invention concerns novel 2-dialkylamino propane derivatives of the formula: ##EQU1## wherein either, R 1  and R 2  are each alkyl; R 3  is hydrogen or alkyl; Q is --OM, wherein M is hydrogen or a cation, --OR 4 , wherein R 4  is alkyl or unsubstituted or substituted phenyl or --NR 5  R 6 , wherein R 5  is hydrogen, alkyl or unsubstituted or substituted phenyl and R 6 , independently has one of the significances of R 5  or is --NHR 7 , wherein R 7  is hydrogen and n is an integer 1, 2 or 3, in free base or acid addition salt form. 
     The compounds possess plant growth regulating and herbicidal properties and are accordingly useful in agriculture.

The present invention relates to 2-dialkylamino propane derivatives andmore specifically to 2-dialkylamino propane, 1,3-disubstituted bydithialkylacyl groups, indicated for agricultural use as plant growthregulators and herbicides.

Accordingly, the present invention provides compounds of formula I,##STR1## wherein either, R₁ and R₂ are each, independently, alkyl (C₁-C₅),

or, R₁ and R₂, together with the nitrogen atom to which they are bound,form a 5 or 6 membered nitrogen containing heterocyclic ring which apartfrom the nitrogen atom may contain a further hetero atom, e.g. nitrogenor oxygen,

R₃ is hydrogen or alkyl (C₁ or C₂),

Q is --OM

wherein M is hydrogen or a cation,

--OR₄

wherein R₄ is alkyl (C₁ --C₈), phenyl, or phenyl substituted by halogen,nitro, alkoxy (C₁ -C₅), phenoxy, carboxy, alkoxycarbonyl (C₂ --C₆)and/or carboxamido or

--NR₅ R₆

wherein R₅ is hydrogen, alkyl (C₁ -C₅), phenyl or phenyl substituted byhalogen, nitro, alkoxy (C₁ -C₅), phenoxy, carboxy, alkoxycarbonyl (C₂-C₆) and/or carboxamido

And R₆, independently, has one of the significances of R₅ or is --NHR₇

wherein R₇ is hydrogen or alkyl (C₁ -C₅)

and n is an integer 1, 2 or 3,

In free base of acid addition salt form.

By the term "halogen" as employed herein is meant fluorine, chlorine orbromine, preferably fluorine or chlorine, especially chlorine.

When any of R₁, R₂, R₃, R₄, R₅, R₆ and R₇ are or contain an alkyl group(e.g. alkoxy), this may be straight or branched chain, primary,secondary or tertiary. Preferably such alkyl or alkyl containing groupscontain 1 to 4, more preferably 1 to 3 carbon atoms, e.g. methyl, ethylor n-propyl.

When R₁ and R₂, together with the nitrogen atom to which they are bound,form a 5 or 6 membered heterocyclic ring, such ring may be saturated orunsaturated, preferably saturated, and may contain a further heteroatomsuch as oxygen or nitrogen. Preferred rings are of the formula ##SPC1##

wherein X is oxygen, --NH--, --CH₂ -- or a direct covalent bond,preferably oxygen, --CH₂ -- or a direct covalent bond, i.e. piperidino,pyrrolidino or morpholino.

When any of R₄, R₅ or R₆ are substituted phenyl, preferably the phenylradical is substituted by 1 to 3 substituents, more preferably by 1 or 2substituents, e.g. 1 substituent, selected from halogen, nitro, alkoxy(C₁ -C₅), phenoxy, carboxy, alkoxycarbonyl (C₂ -C₆) and carboxamido.

When M is a cation, preferably this is an alkali metal, especiallypotassium or sodium, or the ammonium cation.

The present invention also provides a process for the production of acompound of formula I, which comprises

a. condensing a compound of formula II, ##STR2## wherein R₁, R₂ and R₃are as defined above and each X₁ is a leaving group or is potassium orsodium,

with a compound of formula III, ##STR3## wherein n and Q are as definedabove and X₂ is a leaving group or is potassium or sodium,

with the proviso that both X₁ 's are leaving groups and X₂ is sodium orpotassium, or both X₁ 's are sodium or potassium and X₂ is a leavinggroup

or

b. condensing a compound of formula Ia, ##STR4## wherein R₁, R₂, R₃ andn are as defined above and Q₁ is a group --OR₄

wherein R₄ is as defined above,

with a compound of formula IV,

    h--q.sub.2                                                 iv

wherein Q₂ is a group --OM

wherein M is as defined above

or --NR₅ R₆

wherein R₅ and R₆ are as defined as above,

to produce a compound of formula Ib, ##STR5## wherein R₁, R₂, R₃, n andQ₂ are as defined above.

In process variant (a), when each X₁ of formula II is a leaving group,preferred leaving groups are the group

--SO₂ R₈

wherein R₈ is aryl (C₆ -C₁₂), preferably tolyl or phenyl, and the group

--SO₃ M'

wherein M' is potassium or sodium.

Alternatively when X₂ of formula III is a leaving group, preferredleaving groups are chlorine and the group

    --SO.sub.2 R.sub.8

wherein R₈ is as defined above.

The reaction conditions employed in process (a) will to a large extentdepend on the nature of the leaving group in the compounds of formulaeII or III.

For example, when each X₁ is the leaving group --SO₂ R₈, then thereaction may be effected as follows.

The compounds II and III are preferably dissolved in an anhydrousorganic solvent or solvent mixture such as an alcohol, e.g. methanol,ethanol and isopropanol or a nitrile, e.g. acetonitrile, preferablyanhydrous methanol. The reaction is preferably allowed to proceedinitially at room temperature, e.g. for 1 to 2 hours. Subsequently it ispreferred that the reaction mixture is subjected to mild heating, e.g.in the range 25° to 50° C, over a period of, e.g. 1 to 2 hours.Preferably the reaction mixture is stirred.

When each X₁ is the leaving group --SO₃ M', then the reaction may, forexample, be effected as follows viz.

The compound of formula II, suitably in a solvent such as water, ispreferably added, over the course of, for example, compound 15 minutes,to the compounds of formula III dissolved in a solvent, e.g. water.Preferably, the reaction medium comprises a two phase system consistingof an aqueous buffer solution having a pH of about 8, the pH beingmaintained by the addition of mineral acid, preferably hydrochloricacid, and a water immiscible solvent such as ether, benzene, toluene,methylene chloride and chloroform, preferably the latter two.Preferably, the aqueous buffer phase is saturated with a suitable salt,e.g. sodium chloride and/or other reagents such as formaldehyde, for thepurposes of removing and/or binding the sodium sulphite formed duringthe reaction. The mixture is preferably stirred only for a relativelyshort period, e.g. 5 to 10 minutes.

When X₂ is the leaving group R₈ SO₂, then the reaction may, for example,be effected as follows viz.

The compound of formula II, preferably freshly prepared, is preferablydissolved in a suitable anhydrous organic solvent, e.g. anhydrousacetonitrile or chloroform, and the compound of formula III, preferablydissolved in a suitable anhydrous organic solvent, e.g. anhydrousacetonitrile or chloroform, added thereto. Preferably the reactionmixture is maintained at room temperature and stirred.

When X₂ is the leaving group --Cl, then the reaction may, for example,be effected as follows viz:

The compound of formula II, preferably freshly prepared, is preferablydissolved in an appropriate anhydrous organic solvent or solventmixture, e.g. anhydrous chloroform or carbon tetrachloride, and thecompound of formula III preferably dissolved in an anhydrous organicsolvent or solvent mixture, e.g. chloroform or carbon tetrachloride,added thereto. The reaction is preferably effected with stirring, over aperiod of, e.g., 1 to 3 hours. Preferably the reaction is effected in aninert atmosphere, e.g. nitrogen or argon.

In general, working up may be effected in manner known per se.

The reaction conditions, e.g. solvents and temperatures, employed inprocess b), will also, to a large extent depend on the exactsignificance of Q₂ in formula IV.

Thus, when Q₂ is a group --OM, the saponification may be effected inmanner known per se by acid catalysed hydrolysis of the compound offormula Ia. The reaction is accordingly preferably effected bydissolving the compound of formula Ia in a dilute aqueous mineral acid,e.g. 1N sulphuric acid, and heating the reaction mixture, convenientlyto 100° C, over a period of between, e.g. 4 to 5 hours. When salt formsare required, the resulting compound may be reacted with an appropriatebase.

When Q₂ is a group --NR₅ R₆, then the amidation may be effected byaminolysis with a compound of formula HNR₅ R₆ in an appropriate solvent,e.g. acetonitrile, dimethyl formamide, benzene or toluene.

In general, working up may be effected in manner known per se.

The compounds of formulae II and III are either known or may be producedin manner known per se.

Thus, the compounds of formula II, wherein each X₁ is the leaving group--SO₂ R₈ or --SO₃ M', may be produced by reacting a compound of formulaV, ##STR6## wherein R₁, R₂ and R₃ are as defined above and Hal ishalogen, preferably chlorine,

with a compound of formula VI,

    m'sso.sub.2 r.sub.8                                        vi

wherein M' and R₈ are as defined above,

or with potassium or sodium thiosulphate pentahydrate respectively.

The reaction is preferably effected an appropriate solvent, e.g. 50 %aqueous methanol, with heating up to the boiling temperature, e.g. 100°C. If desired, the resulting compound may be employed directly inprocess variant (a) above, e.g., after extraction with an appropriatewater immiscible solvent, e.g. ether, benzene, toluene, methylenechloride or chloroform, preferably the latter two. Alternatively, thecompound of formula I may be isolated, working up being effected inconventional manner.

In addition, the compounds of formula II, wherein each X₁ is a potassiumor sodium cation may be produced from a compound of formula VII,##STR7## wherein R₁, R₂ and R₃ are as defined above, by solvolysis witha sodium or potassium metal alcoholate in the corresponding alcohol,e.g. the methanolate or ethanolate in methanol or ethanol, preferablywith heating, conveniently under reflux. Preferably the reaction iseffected in an inert atmosphere, e.g. nitrogen or argon. After removalof the resulting acetic ester and excess solvent by distillation,preferably in an inert atmosphere, the resulting product may be employeddirectly in process variant a) described above.

Further, the compound of formula III, wherein X₂ is chlorine may beproduced, for example, by reacting a compound of formula VIII, ##STR8##wherein n and Q are as defined above, with chlorine or thionyl chloridein an appropriate solvent such as carbon tetrachloride or chloroform,with stirring and cooling to below room temperature, e.g. to -20° to-30° C, conveniently in the absence of direct sunlight.

The compounds of formulae IV, V, VI, VII and VIII are either known ormay be produced in manner known per se.

In view of the presence of a basic nitrogen atom, the compounds offormula I may exist in free base or acid addition salt forms. Referenceto compounds of formula I herein is intended to embrace all such forms.

Acid addition salt forms of the compounds of formula I may be producedfrom free base forms, e,g, by reaction with an appropriate acid, inmanner known per se and vice versa.

Examples of acids suitable for acid addition salt formation are organicacids such as oxalic acid and inorganic acids such as hydrochloric acid.

The compounds of formula I are colourless or slightly yellow oils orcrystals which may be characterised by their Rf values and/or meltingpoints. Generally, they are readily soluble in polar solvents, e.g.alcohols and nitriles, the compounds of formula I, wherein Q is --OMbeing generally well soluble in water.

The compounds of formula I possess plant growth regulating propertiesand are accordingly indicated for use in agriculture as plant growthregulators.

By the term "plant growth regulating properties" is meant not onlygrowth stimulating or retarding effects in such plant developmentprocesses as blossoming, seeding, fruitation, leafdrop, germination,sprouting and shoot formation but also other changes in the developmentof plant growth such as the known auxin effects, e.g. bending orthickening of the plant parts, e.g. leaves and/or stems, or colourchanges in the leaves, blossoms or fruit.

Thus valuable uses to which plant growth regulators may be appliedinclude inter alia defoliation, accelerated maturity, reduction of fruitset, retardation of blossom, prolongation of the harvesting period andincreased storage stability of the harvested crop or fruit. Plants towhich such plant growth regulating activity may be applied areornamentals, crops such as cotton, hemp, nape, sunflower, maize, corn,tomatoes and vegetables, and in fruit and berry bearing growth.

Apart from their plant growth regulating effects, the compounds alsopossess herbicidal properties and are accordingly indicated for use asherbicides, especially at higher rates of application.

For use as plant growth regulators and also as herbicides, the compoundsare preferably employed for storage and application purposes in the formof a composition in association with a plant growth regulator orherbicide carrier and/or diluent. Such compositions may be either inliquid or solid forms, preferably the former.

Liquid concentrate forms, e.g. emulsion concentrates, i.e. for storageand trade purposes, may comprise solutions of the compound in a solventof comparatively low boiling point, especially alcohols, e.g. ethylalcohol, isopropanol or methyl cyclohexanol, ketones, e.g. acetone orcyclohexanone, hydrocarbons, e.g. toluene or xylene, and/or chlorinatedhydrocarbons, e.g. tetrachloroethane, ethylene chloride ortrichloroethylene. The concentrates may further include surfactants, ifnecessary, to improve the water solubility or emulsion formingproperties of the compounds of formula I. Examples of surfactants arecationic surfactants such as quaternary ammonium compounds, anionicsurfactants such as soaps, long chain aliphatic sulphuric acidmono-esters and salts of long chain alkoxyacetic acids, and non-ionicsurfactants such as polyethylene ethers of fatty alcohols,polyoxyethylene condensation products or particularly, alkarylpolyglycol ethers, e.g. isooctylphenyldecaglycol ether ornonylphenyleikosaglycol ether.

Liquid application forms of the compounds of formula I may be producedby diluting the abovementioned concentrate forms with water to thedesired concentration.

Solid concentrate or application composition forms of the compounds,e.g. dusting, strewing or granulate forms, may be produced by grindingor otherwise mixing the compounds with suitable solid carrier materials.Examples of solid carrier materials are kaolin, talc, chalk, limestoneand cellulose powders. Apart from carrier materials, adjuvants may beincorporated into the solid forms such as surfactants, e.g. to improvethe adhesive properties of the composition with respect to the treatedplants and to improve wettability or dispersibility thereof.

Plant growth regulator or herbicidal compositions may, for example,contain from 1 to 90 %, preferably from 2 to 80 % by weight of thecompound in concentrate forms, and between 0.01 and 10 % by weight ofthe compound in application forms.

The compounds of formula I are applied to the locus to be treated insufficient amount to exert the desired action. The exact amount ofcompound applied will vary depending on, for example, the specificcompound employed, the desired result, ambient conditions and the plantspecies to be treated. In general, however, a plant growth regulatingeffect, e.g. defoliation, may be obtained when applied to a plant locusin an amount in the range 0.1 to 5.0 kg/hectare while a herbicidaleffect may be obtained when applied to a plant or weed locus in anamount in the range 5.0 to 30 kg/hectare, i.e. a plant growth regulatingeffect is generally observed at lower application rates while aherbicidal effect is generally observed at higher application rates.

Two examples of emulsifiable concentrate forms of the compounds of theinvention are described below.

Emulsifiable concentrate (i)

10 parts by weight of a compound of formula I, e.g.5-dimethylamino-2,3,7,8-tetrathianonane-1,9-dioic acid dissolved in 80parts by weight of isopropanol and 10 parts by weight ofisooctylphenyldecaglycol are added thereto as emulsifying agent.

The concentrate is diluted with water to the desired extent forapplication purposes.

Emulsifiable concentrate (ii)

25 parts by weight of a compond of formula I, e.g.dimethyl-(5-morpholino)-2,3,7,8-tetrathianonane-1,9-dioate dissolved in50 parts by weight of acetone and 25 parts by weight ofnonylphenyleikosaglycol ether are added thereto as emulsifying agent.

The concentrate is diluted with water to the desired extent forapplication purposes.

The plant growth regulating and herbicidal properties of the compoundsof formula I are indicated in the following Tests A, B and C.

TEST A: Determination of germination rate, sprout and root growth (cellelongation and cell division) in cucumbers (Cucumis sativus L)

Cucumber seeds are placed on a nybolt net of appropriate mesh size. Thenet touches the surface of a Knop nutrient solution in a plastics cupcontaining the active agents to be tested in doses of 125 p.p.m. (or12.5 p.p.m., marked with ⁺). 16 Seeds are used for each cup. Thegermination rate is determined, the longitudinal growth of the sproutsand roots is measured and other growth effects are visually determinedafter 7 days in comparison with control plants (control plant = 100%.

The results are set out in Table 1 below.

    __________________________________________________________________________                            Sprout                                                                        length                                                                            Root                                                              Germination                                                                           in %                                                                              length                                                            Compared without untreated                                                    control plants after                                          __________________________________________________________________________    Active agent of general 7       Other                                         formula I       1   7   days                                                                              7   effects                                       __________________________________________________________________________    a) Diethyl-(5-dimethylamino)                                                                  108.sup.+                                                                         87.sup.+                                                                           50.sup.+                                                                          63.sup.+                                                                         sprout G1                                     2,3,7,8-tetrathianonane-                                                      1,9-dioate                                                                    b) Hydrogenoxalate of a)                                                                       50.sup.+                                                                         80.sup.+                                                                           50.sup.+                                                                          50.sup.+                                                                         sprout G1A                                    c) Dimethyl-(5-dimethyl-                                                                      100 87  29  29  sprout G1                                     amino)-2,3,7,8-tetra-           root HB                                       thianonane-1,9-dioate                                                         d) Hydrogenoxalate of c)                                                                      90  100 43  43  sprout G1                                                                     root ZHB                                      e) Diisopropyl-(5-dimethyl-                                                                   80  93  29  29  sprout G1                                     amino)-2,3,7,8-tetra-           root B                                        thianonane-1,9-dioate                                                         f) Hydrogenoxalate of e)                                                                      100 87  43  43  sprout G1B                                    g) (5-Dimethylamino-2,3,7,8-                                                                  70  93  29  14  sprout G1                                     tetrathianonane-1,9-dioic-      root B                                        acid                                                                          h) Dimethyl-(5-dimethyl-                                                                          100 50  43  sprout G1                                     amino-5-methyl-2,3,7,8-         root B                                        tetrathianonane-1,9-dio-                                                      ate                                                                           i) Diethyl-(5-dimethyl-                                                                       100 80   0   0                                                amino)-5-methyl-2,3,7,8-                                                      tetrathianonane-1,9-dio-                                                      ate                                                                           j) Diethyl-5-(N-piperidino)-                                                                  100 87  43  38  sprout G1A2                                   2,3,7,8-tetrathianonane-        root B                                        1,9-dioate                                                                    k) Hydrogenoxalate of j)                                                                      100 81  60  33  sprout G1                                     l) Dimethyl-5-(N-piperidino)                                                                  130 100  0   0                                                2,3,7,8-tetrathianonane-                                                      1,9-dioate                                                                    m) Hydrogenoxalate of l)                                                                      110 107 57  43  sprout G1                                                                     root B                                        n) 5-(N-piperidino)-2,3,7,8-                                                                  80  87  43  29  sprout G1                                     tetrathianone-1,9-dioic-        root HB                                       acid                                                                          o) Dimethyl-5-(N-morpholino)                                                                  70  107 43  57  sprout G1                                     2,3,7,8-tetrathianonane-        root B                                        1,9-dioate                                                                    p) Diethyl-5-(N-morpholino)-                                                                  50  87  29  38  sprout G1A2                                   2,3,7,8-tetrathianonane-                                                      1,9-dioate                                                                    q) Hydrogenoxalate of p)                                                                      120 100 57  63  sprout G1BA2                                  r) Diisopropyl-5-(N-morpholi-                                                                 90  107 29  43  sprout G1                                     no)-2,3,7,8-tetrathiano-        root B                                        nane-1,9-dioate                                                               s) 5-(N-morpholino)-2,3,7,8-                                                                      93  50  43  sprout G1                                     tetrathianonane-1,9-dioic-                                                    acid                                                                          t) Dimethyl-5-(N-pyrrolidino)                                                                 90  87  14  29  sprout G1B                                    2,3,7,8-tetrathianonane-        root B                                        1,9-dioate                                                                    u) Diethyl-5-(N-pyrrolidino)-                                                                 90  107 43  29  sprout G1B                                    2,3,7,8-tetrathianonane-        root B                                        1,9-dioate                                                                    v) Diisopropyl-5-(N-pyrroli-                                                                  90  100 43  14  sprout G1                                     dino)-2,3,7,8-tetrathiano-      root B                                        nane-1,9-dioate                                                               w) 5-Dimethylamino-2,3,7,8-                                                                   120 100 71  50  sprout G1                                     tetrathianonane-1,9-dioic-                                                    N,N'-isopropylamide                                                           x) Diethyl-(6-dimethylamino-                                                                      60  17  24  sprout G1                                     3,4,8,9-tetrathiaundecane-      root B                                        1,11-dioate                                                                   y) Diisooctyl-(6-dimethyl-                                                                    70  93  29  14  sprout G1B                                    amino-3,4,8,9-tetrathia-        root B                                        undecane-1,11-dioate                                                          z) Diethyl-6-(N-morpholino)-                                                                      87  33  29  sprout G1                                     3,4,8,9-tetrathiaundecane-      root B                                        1,11-dioate                                                                   __________________________________________________________________________     The abbreviations, used in column "other effects", signify:                   G1 = inhibited growth of leaves                                               A = auxin effect: bendings, thickenings in the whole plant                    A2 = auxin effect along the stems                                             B = burns                                                                     H = inhibited sprouting of lateral shoots or lateral roots                    Z = destruction of final bud or main root vegetation point               

The active agents, referred to in Test A above as compounds (c), (d),(e), (f), (g), (h), (i), (j), (k), (l), (m), (n), (o), (p), (q), (s),(x), (y) and (z), particularly those of (c), (g) and (f), also exhibit aherbicidal effect under the conditions of the Test.

TEST B: Determination of germination rate and sprout growth in cress(Lepidium sativum L)

6 Plastics pots of 7 cm in diameter are filled with sterilized peatculture substrate and sand and then sprayed with 20 cc of sprayingliquor at concentrations of (a) 8,000, (b) 4,000, (c) 2,000, (d) 1,000,(e) 500, (f) 250, (g) 125, (h) 62.5 p.p.m. of active agent of generalformula I.

1 To 2 hours after treatment, 20 cress seeds are sown on the treatedsoil surface. The pots are transferred to climate cabinets and kept at25° C under luminescent lighting (6000 to 8000 lux). After 21 days thegermination rate and the longitudinal growth of the sprouts aredetermined. Other growth effects are visually determined in comparisonwith control plants. The activity index is indicated as follows:##EQU2##

The results are set out in Table 2 below.

                  TABLE 2                                                         ______________________________________                                                                smallest plant                                        Active agent                                                                              smallest herbici-                                                                         growth regulator                                      of general  dal concentra-                                                                            concentration in                                                                          activity                                  formula I   tion in p.p.m.                                                                            p.p.m.      index                                     ______________________________________                                        Dimethyl-                                                                     (5-morpholi-                                                                  no)-3,4,8,9-                                                                              2000        ≦62,5                                                                              ≧32                                tetrathia-                                                                    sebacoate                                                                     Diisooctyl-                                                                   (6-dimethyl-                                                                  amino)-3,4,8,-                                                                            1000        ≦62,5                                                                              ≧16                                9-tetrathia-                                                                  undecane-1,11-                                                                dioate                                                                        5-Piperidino-                                                                 2,3,7,8-tetra-                                                                            500         ≦62,5                                                                              ≧8                                 thianonane-1,-                                                                9-dioic acid                                                                  Hydrogenoxala-                                                                te of dimethyl-                                                               (5-dimethyl-                                                                              500         ≦62,5                                                                              ≧8                                 amino)-2,3,7,8-                                                               tetrathianona-                                                                ne-1,9-dioate                                                                 5-Dimethyl-                                                                   amino-2,3,7,8-                                                                            500         ≦62,5                                                                              ≧8                                 tetrathianona-                                                                ne-1,9-dioic                                                                  acid                                                                          ______________________________________                                    

TEST C: Defoliant test with cotton plants (Gossypium hirsutum) in thepost-emergence process

Culture flasks of 15 × 13 × 8 cm in diameter are filled with sterilizedpeat culture substrate and sand. 8 Cotton seeds are then sown on thesoil surface and kept at 25° C for approximately 3 weeks. When thecotyledones are well developed, the number of the plants is reduced to 5uniformly grown plants for each flask. 5 cc Of a spraying liquor,containing (a) 8,000, (b) 4,000 and (c) 2,000 p.p.m. of active agent ofgeneral formula I, are sprayed on each vessel.

After 27 days, the percentage of the dropped cotyledones is visuallydetermined in comparison with the untreated control plants.

The results are set out in Table 3 below.

                  TABLE 3                                                         ______________________________________                                                                   % of dropped                                                                  cotyledones per                                    Active agent of            5 plants                                           general formula I                                                                            Concentration                                                                             (control = 0)                                      ______________________________________                                        Dimethyl-(5-   a           100                                                morpholino)-2,3,7,-                                                                          b           40                                                 8-tetrathianona-                                                                             c           30                                                 ne-1,9-dioate                                                                 untreated               0                                                     ______________________________________                                    

Of particular interest as plant growth regulators are the compounds offormula I, wherein R₁ and R₂, together with the nitrogen atoms to whichthey are bound form a heterocycle, notably the compounds of formula Ib,##SPC2##

wherein R₃, Q and n are as defined above,

particularly the compounds of formula Ib' ##SPC3##

wherein R₃, R₄ and n are as defined above,

especially the compounds of formula Ib or Ib', wherein n is 1 or 2.

Of particular interest as herbicides are the compounds of formula Ic,##STR9## wherein R₃, Q and n are as defined above and R₁ ' and R₂ ' areeach, independently, alkyl (C₁ -C₅),

particularly the compounds of formula Ic', ##STR10## wherein R₁ ', R₂ ',R₃, M and n are as defined above, especially the compounds of formulaeIc and Ic', wherein n is 1 or 2.

In general, acid addition salt forms of the compounds of formula Iexhibit the same order of activity as the free base forms.

The following Examples illustrate the production of the compounds ofgeneral formula I. All temperatures are indicated in degrees centigradeand all parts and percentages are by weight.

EXAMPLE 1: Diethyl-(5-dimethylamino)-2,3,7,8-tetrathianonane-1,9-dioate##STR11##

45.9 g (0.1 mol) of1,3-bis-(p-toluenesulphonylthio)-2-dimethylaminopropane are suspended in200 cc of absolute methanol. A methanolic solution of 0.2 mol of thesodium salt of mercaptoethyl acetate, produced by dissolving 4.6 g (0.2mol) of sodium in 100 cc of absolute methanol and adding 24.2 g (0.2mol) of mercaptoethyl acetate, is added dropwise with stirring over thecourse of 2 hours, at room temperature. The reaction mixture is kept atroom temperature for one further hour, heated to 50° and stirred forapproximately one further hour. After cooling to room temperature, theprecipitated potassium-p-toluenesulphinate is filtered off and thesolvent evaporated in a vacuum. The residue is taken up in chloroformand washed twice with 100 cc amounts of water. The chloroform solutionis dried with sodium sulphate and then evaporated in vacuum. Theresulting oil may be liberated from the slightly volatile constituentsby heating to 50° over the course of 30 minutes in a high vacuum.

    ______________________________________                                        Analysis:                                                                             C.sub.13 H.sub.25 NO.sub.4 S.sub.4                                                         Molecular weight:                                                                           387.6                                      Calc.  C 41.3 %   H 6.5 %   N 3.6 % S 33.1 %                                  Found  41.6 %     6.7 %     3.7 %   32.9 %                                    ______________________________________                                    

EXAMPLE 2: Hydrogenoxalate ofdiethyl-(5-dimethylamino)-2,3,7,8-tetrathianonane-1,9-dioate

7.6 g (0.2 mol) ofdiethyl-(5-dimethylamino)-2,3,7,8-tetrathianonane-1,9-dioate aredissolved in 30 cc of absolute ethanol. A solution of 2 g (0.22 mol) ofandydrous oxalic acid in 30 cc of absolute ether is added thereto. Theprecipitated hydrogenoxalate is suction filtered, washed with absoluteether and dried at 40° in a high vacuum. Colourless crystals, having aM.P. of 82°, are obtained.

    ______________________________________                                        Analysis:                                                                             C.sub.15 H.sub.27 NO.sub.8 S.sub.4                                                         Molecular weight:                                                                           477.6                                      Calc.  C 37.7 %   H 5.7 %   N 2.9 % S 26.9 %                                  Found  36.8 %     5.5 %     3.0 %   26.5 %                                    ______________________________________                                    

EXAMPLE 3: (5-Dimethylamino)-2,3,7,8-tetrathianonane-1,9-dioic acid##STR12##

10 g (0.026 mol) ofdiethyl-(5-dimethylamino)-2,3,7,8-tetrathianonane-1,9-dioate produced inaccordance with Example 1, are added to 100 cc of 1N sulphuric acid andthe mixture is stirred at 100° until a clear solution is obtained(approximately 4 to 5 hours). After cooling, the reaction solution isneutralized with 100 cc of 1N sodium hydroxide solution and evaporatedto dryness in a vacuum. The dry residue is extracted with 150 cc ofabsolute methanol. After evaporation in a vacuum, then in a high vacuumat 50°, a slightly coloured glassy mass is obtained from the methanol.

    ______________________________________                                        Analysis:                                                                              C.sub.9 H.sub.17 NO.sub.4 S.sub.4                                                        Molecular weight:                                                                            331.5                                      Calc.  C 32.6 %   H 5.2 %   N 4.2 % S 38.7 %                                  Found  32.2 %     5.2 %     4.0 %   38.4 %                                    ______________________________________                                    

EXAMPLE 4:Dimethyl-(5-dimethylamino-5-methyl)-2,3,7,8-tetrathianonane-1,9-dioate##STR13##

23.6 g (0.05 mol) of1,3-bis-(p-toluenesulphonylthio)-2-dimethylamino-2-methylpropane aresuspended in 200 cc of absolute methanol. A methanolic solution of 0.11mol of the sodium salt of the mercaptomethyl acetate, -- produced bydissolving 2.5 g (0.11 mol) of sodium in 100 cc of absolute methanol andadding 11.7 g (0.11 mol) of mercaptomethyl acetate, -- is added dropwisewith stirring to the suspension at room temperature over the course of 2hours. The reaction mixture is kept at room temperature for one furtherhour, then heated to 50° and stirred for approximately one further hour.After cooling to room temperature, the precipitatedpotassium-p-toluenesulphinate is filtered off and the solvent isevaporated in a vacuum. The residue is taken up in chloroform and washedtwice with 100 cc amounts of water. The chloroform solution is driedwith sodium sulphate and then evaporated in a vacuum.

The resulting oil may be liberated from the slightly volatileconstituents by heating to 50° over the course of 30 minutes in a highvacuum.

    ______________________________________                                        Analysis:                                                                             C.sub.12 H.sub.23 NO.sub.4 S.sub.4                                                         Molecular weight:                                                                           373.6                                      Calc.  C 38.6 %   H 6.2 %   N 3.7 % S 34.3 %                                  Found  39.1 %     6.3 %     3.5 %   33.9 %                                    ______________________________________                                    

EXAMPLE 5: Hydrogenoxalate ofdimethyl-(5-piperidino)-2,3,7,8-tetrathianonane-1,9-dioate ##SPC4##

36 g (0.072 mol) of1,3-bis-(p-toluene-sulphonylthio)-2-piperidinopropane are suspended in200 cc of absolute methanol. A methanolic solution of 0.144 mol of thesodium salt of mercaptomethyl acetate, produced by dissolving 3.3 g(0.144 mol) of sodium in 100 cc of absolute methanol and adding 15.3 g(0.144 mol) of mercaptomethyl acetate, is added dropwise with stirringat room temperature over the course of 2 hours. The reaction is kept atroom temperature for one further hour, heated to 50° and stirred forapproximately one further hour. After cooling to room temperature, theprecipitated potassium-p-toluenesulphinate is filtered off and thesolvent evaporated in a vacuum. The residue is taken up in chloroformand washed twice with 100 cc amounts of water. The chloroform solutionis dried with sodium sulphate and then evaporated in a vacuum. A viscousoil is obtained.

The hydrogenoxalate is produced by dissolving 8 g of the obtained oil in30 cc of absolute ether and adding thereto a solution of 2 g ofanhydrous oxalic acid in 30 cc of absolute ether. The precipitatedhydrogenoxalate is suction filtered, washed with absolute ether anddried at 40° in a high vacuum.

Colourless crystals, having a M.P. of 183°-185°, are obtained.

    ______________________________________                                        Analysis:                                                                             C.sub.16 H.sub.27 NO.sub.8 S.sub.4                                                         Molecular weight:                                                                           489.6                                      Calc.  C 39.2 %   H 5.6 %   N 2.9 % S 26.2 %                                  Found  40.1 %     5.8 %     3.1 %   25.9 %                                    ______________________________________                                    

EXAMPLE 6:Dioctyl-(6-dimethylamino)-3,4,8,9-tetrathiaundecane-1,11-dioate##STR14##

45.9 g (0.1 mol) of1,3-bis-(p-toluenesulphonylthio)-2-dimethylaminopropane are suspended in200 cc of absolute methanol. A methanolic solution of 0.2 mol of thesodium salt of the isooctyl 3-mercaptopropionic acid, produced bydissolving 4.6 g (0.2 mol) of sodium in 100 cc of absolute methanol andadding 43.6 g (0.2 mol) of isooctyl 3-mercaptopropionic acid, is addeddropwise with stirring at room temperature over the course of 2 hours.The reaction mixture is kept at room temperature for one further hour,heated to 50° and stirred for approximately one further hour. Aftercooling to room temperature, the precipitatedpotassium-p-toluenesulphinate is filtered off and the solvent evaporatedin a vacuum. The residue is taken up in chloroform and washed twice with100 cc amounts of water. The chloroform solution is dried with sodiumsulphate and then evaporated in a vacuum.

The resulting oil may be liberated from the slightly volatileconstituents by heating to 50° over the course of 30 minutes in a highvacuum.

    ______________________________________                                        Analysis:                                                                              C.sub.27 H.sub.53 NO.sub.4 S.sub.4                                                         Molecular weight:                                                                           584                                       Calc.  C 55.5 %   H 9.1 %   N 2.4 % S 22.0 %                                  Found  54.9 %     8.8 %     2.4 %   21.8 %                                    ______________________________________                                    

EXAMPLE 7: 5-Dimethylamino-2,3,7,8-tetrathianonane-1,9-dioicdi-N,N'-isopropylamide ##STR15##

23 g (0.05 mol) of1,3-bis-(p-toluenesulphonylthio)-2-dimethylaminopropane are suspended in300 cc of absolute acetonitrile. A suspension of 0.11 mol of the sodiumsalt of the mercaptoacetic isopropylamide, produced by boiling 17.5 g(0.11 mol) of acetylthioacetic isopropylamide in 300 cc of absoluteacetonitrile for 4 hours and adding 6.0 g (0.11 mol) of sodiummethylate, is added dropwise with stirring at room temperature over thecourse of 2 hours. The reaction mixture is kept at room temperature forone further hour, heated to 50° and stirred for approximately onefurther hour. After cooling to room temperature, the precipitatedpotassium-p-toluenesulphinate is filtered off and the solvent evaporatedin a vacuum. The residue is taken up in chloroform and washed twice with100 cc amounts of water. The chloroform solution is dried with sodiumsulphate and then evaporated in a vacuum. The residue is recrystallizedfrom acetic ester and colourless crystals, having a M.P. of 114°, areobtained.

    ______________________________________                                        Analysis:                                                                              C.sub.15 H.sub.31 N.sub.3 O.sub.2 S.sub.4                                                  Molecular weight:                                                                           413.7                                     Calc.  C 43.6 %   H 7.6 %   N 10.2 %                                                                              S 31.0 %                                  Found  43.8 %     7.5 %     10.4 %  30.6 %                                    ______________________________________                                    

The compounds of general formula I, indicated in the following Table,may be produced in manner analogous to that described in Examples 1 to7.

    __________________________________________________________________________                                                  Analysis                                                                      Calc.                           Example                           Empirical formula                                                                         Found                           No.  R.sub.1                                                                           R.sub.2                                                                           R.sub.3                                                                           Q       n  Salt  Molecular weight                                                                          C  H N S   M.P.                 __________________________________________________________________________     8   CH.sub.3                                                                          CH.sub.3                                                                          H   --OCH.sub.3                                                                           1  --    C.sub.11 H.sub.21 NO.sub.4 S                                                              36,7                                                                             5,9                                                                             3,9                                                                             35,7                                                       359,5       36,3                                                                             5,8                                                                             3,4                                                                             34,9                      9   CH.sub.3                                                                          CH.sub.3                                                                          H   --OCH.sub.3                                                                           1  Hydrogen-                                                                           C.sub.11 H.sub.21 NO.sub.4 S.sub.4.C.sub                                      .2 H.sub.2 O.sub.4                                                                        34,7                                                                             5,2                                                                             3,1                                                                             28,5                                                                              77-78°                                    oxalate                                                                             449,6       34,8                                                                             5,2                                                                             3,6                                                                             29,0                     10   CH.sub.3                                                                          CH.sub.3                                                                          H   --O--i--C.sub.3 H.sub.7                                                               1  --    C.sub.15 H.sub.21 NO.sub.4 S.sub.4                                                        43,3                                                                             7,0                                                                             3,4                                                                             30,9                                                       415,7       43,2                                                                             7,0                                                                             3,2                                                                             30,4                     11   CH.sub.3                                                                          CH.sub.3                                                                          H   --O--i--C.sub.3 H.sub.7                                                               1  Hydrogen-                                                                           C.sub.15 H.sub.21 NO.sub.4 S.sub.4.C.sub                                      .2 H.sub.5 O.sub.5                                                                        40,4                                                                             6,2                                                                             2,8                                                                             25,4                                                                              165°                                      oxalate                                                                             505,7       39,7                                                                             5,9                                                                             3,0                                                                             25,8                     12   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          --OC.sub.2 H.sub.5                                                                    1  --    C.sub.14 H.sub.27 NO.sub.4 S.sub.4                                                        41,9                                                                             6,8                                                                             3,5                                                                             31,9                                                       401,7       41,2                                                                             6,4                                                                             3,5                                                                             32,4                     13   N-Piperidino                                                                           H  --OC.sub.2 H.sub.5                                                                    1  --    C.sub.16 H.sub.29 NO.sub.4 S.sub.4                                                        44,9                                                                             6,8                                                                             3,3                                                                             30,0                                                       427,7       43,8                                                                             6,6                                                                             3,5                                                                             30,6                     14   N-Piperidino                                                                           H  --OC.sub.2 H.sub.5                                                                    1  Hydrogen-                                                                           C.sub.16 H.sub.29 NO.sub.4 S.sub.4.C.sub                                      .2 H.sub.2 O.sub.4                                                                        41,8                                                                             6,0                                                                             2,7                                                                             24,8                                                                              178-180°                                  oxalate                                                                             517,7       42,3                                                                             6,0                                                                             2,9                                                                             23,9                     15   N-Piperidino                                                                           H  --OH    1  --    C.sub.12 H.sub.21 NO.sub.4 S.sub.4                                                        38,8                                                                             5,7                                                                             3,8                                                                             34,5                                                       371,6       37,9                                                                             6,0                                                                             3,6                                                                             34,2                     16   N-Piperidino                                                                           H  --OCH.sub.3                                                                           1  --    C.sub.14 H.sub.25 NO.sub.4 S.sub.4                                                        42,1                                                                             6,3                                                                             3,5                                                                             32,1                                                       399,6       42,3                                                                             6,2                                                                             3,2                                                                             31,8                     17   N-Morpholino                                                                           H  --OC.sub.2 H.sub.5                                                                    1  --    C.sub.15 H.sub.27 NO.sub.5 S.sub.4                                                        41,9                                                                             6,3                                                                             3,3                                                                             29,9                                                       429,6       41,0                                                                             6,2                                                                             3,4                                                                             30,9                     18   N-Morpholino                                                                           H  --OC.sub.2 H.sub.5                                                                    1  Hydrogen-                                                                           C.sub.15 H.sub.27 NO.sub.5 S.sub.4.C.sub                                      .2 H.sub.2 O.sub.4                                                                        39,3                                                                             5,6                                                                             2,7                                                                             24,7                                                                              191°                                      oxalate                                                                             519,6       39,1                                                                             5,5                                                                             2,9                                                                             23,8                     19   N-Morpholino                                                                           H  --OCH.sub.3                                                                           1  --    C.sub.13 H.sub.23 NO.sub.5 S.sub.4                                                        38,9                                                                             5,8                                                                             3,5                                                                             31,9                                                       401,6       39,2                                                                             5,9                                                                             3,7                                                                             31,2                     20   N-Morpholino                                                                           H  OH      1  --    C.sub.11 H.sub.19 NO.sub.5 S.sub.4                                                        35,4                                                                             5,1                                                                             3,7                                                                             34,3                                                       373,5       34,8                                                                             5,2                                                                             3,2                                                                             33,8                     21   N-Morpholino                                                                           H  --O--i--C.sub.3 H.sub.7                                                               1  --    C.sub.17 H.sub.31 NO.sub.5 S.sub.4                                                        44,6                                                                             6,8                                                                             3,1                                                                             28,0                                                       457,7       44,7                                                                             6,8                                                                             3,0                                                                             27,1                     22   N-Pyrrolidino                                                                          H  --OC.sub.2 H.sub.5                                                                    1  --    C.sub.15 H.sub.27 NO.sub.4 S.sub.4                                                        43,6                                                                             6,6                                                                             3,4                                                                             31,0                                                       413,6       42,8                                                                             6,4                                                                             3,4                                                                             31,5                     23   N-Pyrrolidino                                                                          H  --OCH.sub.3                                                                           1  --    C.sub.13 H.sub.23 NO.sub.4 S.sub.4                                                        40,5                                                                             6,0                                                                             3,6                                                                             33,3                                                       385         39,5                                                                             5,9                                                                             3,5                                                                             32,8                     24   N-Pyrrolidino                                                                          H  --O--i--C.sub.3 H.sub.7                                                               1  --    C.sub.17 H.sub.31 NO.sub.4 S.sub.4                                                        46,2                                                                             7,1                                                                             3,2                                                                             29,0                                                       441         46,2                                                                             6,9                                                                             3,2                                                                             29,6                     25   N-Pyrrolidino                                                                          H  --O--i--C.sub.3 H.sub.7                                                               1  Hydrogen-                                                                           C.sub.17 H.sub.31 NO.sub.4 S.sub.4.C.sub                                      .2 H.sub.2 O.sub.4                                                                        42,9                                                                             6,3                                                                             2,6                                                                             24,1                                                                              181°                                      oxalate                                                                             531,7       41,9                                                                             6,0                                                                             3,0                                                                             23,8                     26   CH.sub.3                                                                          CH.sub.3                                                                           H  --OC.sub.2 H.sub.5                                                                    2  --    C.sub.15 H.sub.29 NO.sub.4 S.sub.4                                                        43,3                                                                             7,0                                                                              3,4                                                                            30,9                                                       415,7       43,8                                                                             7,0                                                                             3,5                                                                             30,2                     27   N-Morpholino                                                                           H  --OC.sub.2 H.sub.5                                                                    2  --    C.sub. 17 H.sub.31 NO.sub.5 S.sub.4                                                       44,6                                                                             6,8                                                                             3,1                                                                             28,0                                                       457,7       45,1                                                                             6,8                                                                             2,8                                                                             26,7                     __________________________________________________________________________

What is claimed is:
 1. A compound of the formula: ##SPC5##wherein X isoxygen, --NH--, --CH₂ -- or a direct covalent bond, R₃ is hydrogen or C₁or C₂ alkyl, n is 1, 2 or 3, Q is --OM, --OR₄ or --NR₅ R₆, M ishydrogen, an alkali metal cation or the ammonium cation, R₄ is C₁ to C₈alkyl, phenyl or phenyl mono-, di- or tri-substituted independently byfluoro, chloro, bromo, C₁ to C₅ alkoxy, phenoxy, carboxy, C₂ to C₆alkoxycarbonyl or carboxamido, R₅ is hydrogen, C₁ to C₅ alkyl, phenyl orphenyl mono-, di- or tri-substituted independently by fluoro, chloro,bromo, nitro, C₁ to C₅ alkoxy, phenoxy, carboxy, C₂ to C₆ alkoxycarbonylor carboxamido, R₆ is --NHR₇ or independently R₅, and R₇ is hydrogen orC₁ to C₅ alkyl,or an acid addition salt thereof.
 2. A compound of claim1, of the formula: ##SPC6##wherein R₃, Q and n are as defined inclaim
 1. 3. A compound of claim 2, of the formula: ##SPC7##wherein R₃,R₄ and n are as defined in claim
 2. 4. A compound according to claim 1,wherein n is 1 or
 2. 5. The compound of claim 1, which isdimethyl(5-piperidino)-2,3,7,8-tetrathianonane-1,9-dioate.
 6. Thecompound of claim 1, which isdimethyl(5-piperidino)-2,3,7,8-tetrathianonane-1,9-dioate in hydrogenoxalate form.
 7. The compound of claim 1, which isdiethyl(5-piperidino)-2,3,7,8-tetrathianonane-1,9-dioate.
 8. Thecompound of claim 1, which isdiethyl(5-piperidino)-2,3,7,8-tetrathianonane-1,9-dioate in hydrogenoxalate form.
 9. The compound of claim 1, which is5-piperidino-2,3,7,8-tetrathianonane-1,9-dioic acid.
 10. The compound ofclaim 3, which isdiethyl(5-morpholino)-2,3,7,8-tetrathianonane-1,9-dioate.
 11. Thecompound of claim 3, which isdiethyl(5-morpholino)-2,3,7,8-tetrathianonane-1,9-dioate in hydrogenoxalate form.
 12. The compound of claim 3, which isdimethyl(5-morpholino)-2,3,7,8-tetrathianonane-1,9-dioate.
 13. Thecompound of claim 2, which is5-morpholino-2,3,7,8-tetrathianonane-1,9-dioic acid.
 14. The compound ofclaim 3, which isdi-isopropyl-(5-morpholino)-2,3,7,8-tetrathianonane-1,9-dioate.
 15. Thecompound of claim 1, which isdiethyl(5-pyrrolidino)-2,3,7,8-tetrathianonane-1,9-dioate.
 16. Thecompound of claim 1, which isdimethyl(5-pyrrolidino)-2,3,7,8-tetrathianonane-1,9-dioate.
 17. Thecompound of claim 1, which isdi-isopropyl-(5-pyrrolidino)-2,3,7,8-tetrathianonane-1,9-dioate.
 18. Thecompound of claim 1, which isdi-isopropyl-(5-pyrrolidino)-2,3,7,8-tetrathianonane-1,9-dioate inhydrogen oxalate form.
 19. The compound of claim 3, which isdiethyl(6-morpholino)-3,4,8,9-tetrathiaundecane-1,11-dioate.